Aldehyde hydrogenation catalyst preparation



March 1961 R. B. MASON ETAL 2,976,254

ALDEHYDE HYDROGENATION CATALYST PREPARATION Original Filed Aug. 21, 1953 1 k\\ 1 I I q 4 I s s ALDEHYDE+ 3 PRODUCT 2 By W Attorney United States Patent Dfifice Patented Mar. 21, 1961 ALDEHYDE HYDROGENATION CATALYST PREPARATION Original application Aug. 21,1953, Ser. No. 375,591,

now Patent No. 2,813,911, dated Nov. 19, 1957. Divided and this application Feb. 8, 1957, Ser. No. 638,938

3 Claims. (Cl. 252-439) The present invention relates to an improved process for preparing sulfur-insensitive hydrogenation catalysts, especially adaptable to the hydrogenation of x0 aldehydes, to increase activity of the catalysts and decrease the extent of contaminants andimpuritiesin the resulting alcohol product. 7

The synthesis of oxygenated organic compounds from olefinic compounds and mixtures of CO and H in the presence of acatalyst containing metals of the iron group, particularly cobalt, is now well known. In the first stage, the olefinic material, catalyst, and CO and H are reacted at superatmospheric pressures to give a. product consistingessentially of aldehydes containing one more carbon atom than the reacted olefin. This oxygenated organic mixture, which contains in solution salts and carbonyls of the catalyst, i.e. cobalt carbonyl, is treated in a catalyst removal zone at elevated temperatures to cause removal of the metal carbonyls. The catalyst-free material is, then hydrogenated to the corresponding. alcohol, and it is to this stage that the present invention applies.

This carbonylation reaction. produces a particularly attractive method for preparing valuable primary alcohols, particularly those which are intermediates for plasticizers and detergents. Amenable to the reaction are substantially all types of organic compounds, substituted or not, which contain olefinic unsaturation.

The catalyst for the first stage of the reaction, where olefinic material is converted into aldehyde, is usually added in the form of salts of the catalytically active metal with high molecularweightorganic acids, such as oleic, stearic', naphthentic, etc.. Examples of such catalyst salts or soaps are cobalt stearate, naphthenate and the like. These salts are soluble inthe liquid olefin or olefin-paraflin feed, and may be suppliedtothe first stage, dissolved in the feed or as'hydrocarbon solution. 1

As the synthesis gases are consumed at equivalent or equimolar rates, synthesis gas components are usually added at equimolar proportions of H and CO, though it has been suggested to use both an excess of hydrogen and an excess of CO. The conditions for reacting olefinic compounds with hydrogen and carbon monoxide vary somewhat in accordance with the naturegof the olefinic "feed, but the reaction is generally conducted at pressures of about 3000 pounds'per sq. in. and attemf peratures in the range of about 200 to 450 F. The

ratiov of synthesis gas feed to olefin may vary widely; in general, about 1000, to 15,000 cu. ft. of H +CO per barrelof-oleiin feed are employed.

,Following the carbonylation stage, not containing in solution a considerable amount of dissolved catalyst-in the form of carbonyls, is treated at elevated temperatures in the presence fofa gas, vapor, or liquid to decompose the carbonyl to an'oil-insoluble form of the metal. 'Thereafter, the aldehyde product is freed of suspended catalyst, and is passed to a hydrogenation zone for conversion into alcohols.

The hydrogenation stage. may be operated at v condi the aldehyde. prod 2 tions including temperatures and pressures and feed rates of the same order of magnitude as those obtaining'in the carbonylation stage. Various types of catalysts may be employed in the reaction. However, serious difiiculties have been encountered in the hydrogenation catalyst, when sulfur-sensitive catalysts, such as nickel and the like are employed in this service. The most readily available olefinic feed stocks are selected hydrocarbon streams derived from petroleum sources, and these frequently have sulfur contents of 0.1% and even higher. Similarly, the synthesis gases employed in the carbonylation zone are frequently contaminated with minor amounts of sulfur impurities.

Appreciable sulfur which is present in the crude reaction mixture containing the carbonyl compounds is carried through the oxonation and carbonylation stage into the hydrogenation stage, where it combines with the hydrogenation catalyst, if the latter is sulfur-sensitive, to reduce and destroy its activity.

Extensive experimental work with sulfur-insensitive catalysts showed that the great majority either had unsatisfactory activity or alcohol selectivity, or had insuificient mechanical strength, or all of these undesirable properties. However, it was found that a catalyst consisting essentially of molybdenum sulfide supported on activated carbon combined satisfactory mechanical strength with good activity and high alcohol selectivity, and was far superior to other sulfur-insensitive hydrogenation cat alysts for liquid phase hydrogenation of sulfur-contaminated aldehyde product resulting from the carbonylation reaction. The catalyst. was prepared by impregnating activated char, in the form of 4-8 mesh granules, with an aqueous solution of ammonium molybdate, heatedto decompose the molybdate to the corresponding oxide,

MoO and sulfided with H 5 to' convert the oxide to the sulfide. a 7

Though the sulfur-insensitive catalyst thus produced has the great advantage of long life, physical strength and resistance to poisoning by carbon monoxide and sulfur, it suifers the disadvantage of permitting some sulfur to pass unchanged through the hydrogenation zone. Eur-1 thermore, it has been observed that when the catalystis freshly sulfided, there is a pronounced tendency to introduce additional. sulfur into the alcohol product; The amounts are relatively small, in the order of a few parts per million, and, in most operations, as wheredetergent alcohols are to be produced, would cause no ditficulties. But in the case where alcohols are prepared for utilization as plasticizer intermediates, these small amounts of sulfur play an important role in degrading the product and making it unfit for use as a plasticizer. In particucolorless resins and clear plastics that theybe substan product under reduced pressures andblendedfwithfr' v alcohol for recycle to the esterification zoneri e lar, the octyl and nonyl alcohols are favored as plasti cizing-agents in. the form of their esters, such as phthalates, adipates, maleates and the like. It isa condition precedent that for their use as plasticizers for light or tially colorless.

:It has been typical alcohol recycle es'te'rification operation, a 1 -27 molal excess of alcohol is usedbased onphthalieia dride. -Unreacted'a1cohol is; stripped off from the found thatextremely small amounts of, sulfur in the alcohol product, on the order of less than a thousandth of apercent, are sufiicient to make the al-i cohol unfit for plasticizing purposes. Thusit. has beenfound that where the" alcohol productvhas a sulfur'content of only 15 parts per million, i.'e. .0.O015%; the, 'phthalate esterification product'was too dark "for use as; a plas'ticizing material.,"This darkening occurs during 1 the recycling operation during esterification. 1 Thus in 'a more than about 10 parts per million of sulfur contaminants are present in the alcohol product,'it has been found that color forming bodies build up in the recycle material during the recycle stage.

In brief, therefore, small amounts of sulfur in the alcohol product to be employed in the manufacture of plasticizing intermediates play an important role in degrading the product, resulting in an economic loss. Contamination has been traced in part to liberation of sulfur from the sulfactive molybdenum hydrogenation catalyst in the early stages of the operation. The catalyst is prepared by impregnating carbon pellets with ammonium molybdate or other hexavalent forms of molybdenum, thereafter sulfiding by heating the catalyst in a stream of H to 200 to 400 F. and. then introducing a stream of non-reactive liquid, such as a light virgin naphtha, saturated with H S. The catalyst temperature is then raised to 500 to 900 F. for 12-24 hours until sulfiding is complete, and M converted essentially completely to the sulfide.

-When the catalyst thus prepared is employed in the commercial hydrogenation of aldehydes prepared by carbonylation of C olefins to produce octyl alcohols for use as plasticizing intermediates, it was found, in a particular operation, that the first 20,000 gallons of C alcohols thus produced were completely unsuitable for use as plasticizing agent intermediates. The alcohol product had a sulfur content of 19 parts per million, which was found to produce an ester color of 1.05. The ester color is a measure of optical density of the ester as produced under prescribed conditions, and has been found to be affected by extremely small amounts of sulfur impurities. The wave length used in studying iso octyl phthalate ester is 4470 A. For producing a satisfactory plasticizing ester, the ester color should not be greater than about 0.1. This value is associated with product alcohol sulfur content of 10 parts per million and less.

It is, therefore, the principal object of the present invention to provide and to prepare an aldehyde hydrogenation catalyst which is insensitive to carbon monoxide and sulfur, but which will in turn have less tendency to contaminate the resulting alcohol product than sulfactive catalysts hitherto described.

It is also a purpose and object of the present invention to prepare in a novel manner a superior sulfactive aldehyde hydrogenation catalyst of high activity, which reaches a high activity level at a lower temperature than sulfactive catalysts prepared by means hitherto described in the art.

Other and further purposes, objects and advantages of the present invention will become apparent from the more detailed description hereinafter.

It has now been found that a molybdenum sulfide-oncharcoal catalyst of considerably greater stability and lesser tendency to lose sulfur initially may be prepared by sulfiding a form of molybdenum oxide wherein the molybdenum is in a lower valence state than in the hexavalent form, which has been the practice to sulfide hitherto.

In the standard method of preparing the sulfided catalyst, as described hitherto, activated carbon pellets are impregnated with a hexavalent molybdenum salt, such as ammonium molybdate, and thereafter heated to'convert the material to M00 which is then sulfided. On heat-' ing in the presence of H 8, the oxide is probably converted initially to the trisulfide which decomposes in the presence of heat'to molybdenum disulfide and elementary sulfur. Also, elementary sulfur may result from the re duction of the molybdenum trioxide by the H 8 during the sulfiding stage. In either case, elementary sulfur is left on the catalyst and is gradually removed by the alcohol product during the hydrogenation. This sulfur loss reaches an apparent equilibrium after about 15,000- 20,000 gallons of alcohol have been produced byhydrogenation and, as pointed out, this initial alcoholprodnot is not suitable for esterification purposes, and must be further treated or rerun, after the catalyst has come into equilibrium, because of high sulfur content and high ester color.

It has now been found that the hydrogenation catalyst may be considerably more quickly and efiiciently sulfided, and the amount of off-test alcohol produced in the initial stages of the hydrogenation reaction be appreciably lessened, by reducing the valence of the molybdenum on the catalyst from the hexavalent form to an intermediate state before sulfiding. 'This is done by heating the catalyst after impregnation to about 200 to 350 F.,

' to decompose the ammonium molybdate to molybdenum trioxide, M00 Thereafter, a stream of hydrogen is introduced at a temperature of about 600 to 1000 F., at a pressure of 200-3000 p.s.i.g. for a sutlicient period of time to reduce M00 to M00 M00, or a mixture of the lower oxides. The sulfided catalyst, whether prepared from the higher or lower oxides of molybdenum, consists for the most part of M08 i.e. the molybdenum is in the quadrivalent state. But when the molybdenum is reduced to the quadrivalent state, or lower, prior to sulfiding, as in accordance with the present invention, the oxidation of hydrogen sulfide to elementary sulfur is avoided.

When the desired amount of reduction has been accomplished, the catalyst bed is cooled to about 300 F., and H 8 is introduced into the bed, either as a gas or dissolved in an inert liquid, such as Varsol or virgin naphtha. Gas is passed until sulfiding is complete. Because of the prereduction of the catalyst, a shorter time and less H S are required than when M00 is sulfided.

The present invention and its application will best be understood from the more detailed description hereinafter, wherein reference will be made to the accompany-- ing drawing, which is a schematic representation of a system suitable for carrying out a preferred embodiment of the invention. As the latter resides in the hydrogenation rather than in the carbonylation or finishing stages, only the first mentioned step is shown in the drawing.

Referring now to the drawing, liquid aldehyde product substantially free of dissolved cobalt, and which may contain in solution as much as 0.005% sulfur, is passed to the lower portion of hydrogenator 2 via line 4. Simultaneously, H is supplied to reactor 2 through line 6 in proportions at least sufiicient to convert the aldehyde product into the corresponding alcohol. The catalyst within reactor 2 comprises molybdenum sulfide supported on an active carbon carrier prepared as detailed below, the proportion of molybdenum sulfide to the carrier being about 1 to 10%. Hydrogenator 2 may be operated at pressures of about 2500 to 4500 p.s.i.g., and at temperatures from about 400 to 600 F., a liquid feed rate of from 0.25-2 v./v./hr., and a hydrogen feed rate of from 500020,000 cu. ft./bbl. It is also beneficial to add to the hydrogenation zone up to 810% water.

, The hydrogenation catalyst is preferably first prepared by impregnating W pellets of activated charcoal with ammonium molybdate, and drying in a steam oven at 250 If. The dried product is transferred to hydrogenator 2, and heated to 600 to 1000 F., in a stream of hydrogen admitted through line 8. Pressures of '200- 3000p.s.i.g., are maintained in 2, and the passage of gas is continued until at least part of the M00 formed by the decomposition of the molybdate has been converted to the desired mixture of M00 and M00 the operation may also be controlled to produce substantially either of these oxides; Control of the extent of reduction is readily maintained by collecting and measuring the amount of water formed.

' When the desired amount of reduction has been accomplished, the catalyst bed is cooled to about 200 to 400 F. and thecatalyst sulfided, which may be carried out by passing gaseous H 8 or H 5 dissolved in an inert liquid,

such as Varsol or virgin naphtha, through the bed until sulfidingis. complete. These materials may also be through line 8, after. the hydrogena-' passed into the bed tion has been terminated.

-A-fter sulfiding, the catalyst is allowed tocome to conditions,1the excess sulfiding..agent'. is purged, .and a stream of inert hydrocarbon, such as Varsol, is passed through the bed for several hours. Thereafter, the aldehyde feed is cut in under operating conditions described above.

The products of the hydrogenation reaction are withdrawn overhead through line and passed to the alcohol finishing plant for further processing in a manner known per se.

The process of the present invention and its results may be further illustrated by the following results obtained in a commercial operation wherein isooctyl alcohols were prepared from a heptene fraction. In run A, the catalyst was not reduced prior to sulfiding, while in run B, the catalyst was treated substantially in the manner described heretofore.

The above data clearly show that with the catalyst prepared in accordance with the present invention, the amount of off-test alcohol which required further processing was cut in half, being reduced from 20,000 to 10,000 gallons. Furthermore, the quality of the offtest alcohol initially prepared by the new process was considerably better than that initially prepared by the process employing the catalyst prepared by the former technique and thus requires considerably less reprocessing to make the alcohol suitable for plasticizing purposes.

It is of interest to note that the initially hydrogenated catalyst had a hydrogenation activity equal to that of the non-prehydrogenated catalyst at a considerably lower temperature level. This is a marked advantage. Particularly in the case of the sulfactive catalysts it has been found that at the higher temperatures necessary to get good activity, there is a marked tendency to overhydrogenation and conversion of the aldehyde directly to the hydrocarbon or olefin, due to dehydration of the alcohol initially formed. With the catalyst of the present invention, lower hydrogenation temperatures may be employed, thus minimizing overhydrogenation.

The process of the present invention may be modified in manners apparent to those skilled in the art. Thus, though a hydrogenation catalyst consisting of molybdenum sulfide on activated carbon has beendescribed, the prereducing technique may in general, particularly to those containing chromium, tungsten, cobalt and nickel, all of which may have sulfides existing in more than one valence state. Similarly; the oxides which are to be sulfided maybe formed by other known means beside impregnation. and heating to decompose the soluble salt. Also. the reduction need not he carried out to completion, but it is desirable that the metal component of the catalyst be reduced toa state of oxidation as low as i'nthe sulfide form- Also, other sulfiding agents such asCS may be used.

The treatment of the molybdenum oxide with hydrogen prior to sulfidingcan be employed with any molybdena preparation. For example, a catalyst comprising approxicomprises impregnating preformed activated char pellets Y be applied to sulfide catalysts mately equimolarquantities of molybdenum-- oxide, zinc oxide and magnesium oxide was tested in autoclave opera,- tions after (1) sulfiding without the hydrogen pretreatment and-.(Z) sulfiding followin'g'hydro-gen reduction at 850 F. Data'frorn these'operations are:

Feed Cs Aldehydes from commercial plant +5-6% water Run No O D Catalyst MoOa.ZnO.MgO M0O3.ZDO.MEO. Catalyst Treatment Reduced with Hz Sulfided with H s at 850 F., Sulat 850 F. fided with H 5 at 850 F. Hours of Run 4 Temperature, F Pressure, p.s.i.g-- 2 Product Carbonyl No Product Distribution:

Wt. percent Hydrocarbon. Wt. percent Intermediate. Wt. percent Alcohol 52 Wt. percent Bottoms-.-

To indicate that the amount of sulfur associated with the prereduced catalyst was substantially smallerthan that associated with the same catalyst that was not given the prehydrogenation treatment, the following data are shown:

Commercial Catalyst Of This Preparation Invention Pretreatment 4% Hrs-Nitrogen 8 Hrs-Hydrogen Activation None H S None Hi8 Sulflded Sulfided Temp, F 850 850 Hours 5. 5 6. 5 Analytical Data:

Mo as M003... 9. 4 0.1 10.1 10. 5 Sulfur 0.3 7. 8 0. 3 .6. 5 Calculated Mo/S:

Ratio 1/3.8 1/26 and M00. The final catalyst in both cases, however, was

essentially M08 the difference in sulfur content reflecting and being a measure of the elementary sulfur formed by reduction of the hexavalent molybdenum in run E with H 8.

This application is a filed August 21, 1953, now U.S. Patent 2,813,911.

What is claimed is: 5

1. An improved process for preparing a superior sulfactive molybdenum sulfide hydrogenation catalyst which with an ammonium molybdate solution, drying the pellets, decomposing said molybdate to the oxide, subjecting said xide to a hydrogenation reaction to reduce at least a portion of the metal combined therewith to an oxide of a j lower valence state, and thereafter sulfiding said reduced material.

2. An improved process for preparing sulfactive molyb denum sulfide hydrogenation catalyst which comprises impregnating preformed'activated char pellets. with arrimonium molybdate, heating saidimpregnated material at a temperature of about 200 to 350 F. to decomposesaid salt to the oxide, hydrogenating said oxide at a temper-atu re of. about 600 to 1000 F. and at a pressure of about i f 200-3000 p.s.i.g. for a period sufficient to convert at least a substantial portionofsaid oxide to M00 and thereafter sulfiding said hydrogenated product with a sulfiding agent.

division of Serial No. 375,591, g

7 ,4 V 3. A catalyst prepared in accordance with the process 2,455,713 r claim 2. V v e .-2,s11,4s3 References Cited in the file Of this patefit 251257o UNITED STATES PATENTS 5 2,432,087 Brown Dec. 9, 1947 8 Voorhies Dec. 7, 1948 Barry June 13, 1950 Sartor June 20, 1950 Stiles Dec. 2, 1952 Smith July 12, 1955 

1. AN IMPROVED PROCESS FOR PREPARING A SUPEERIOR SULFACTIVE MOLYBDENUM SULFIDE HYDROGENATION CATALYST WHICH COMPRISES IMPREGNATING PREFORMED ACTIVATED CHAR PELLETS WITH AN AMMONIUM MOLYBDATE SOLUTION, DRYING THE PELLETS, DECOMPOSILNG SAID MOLYBDATE TO THE OXIDE, SUBJECTING SAID OXIDE TO A HYDROGENATION REACTION TO REDUCE AT LEAST A PORTION OF THE METAL COMBINED THEREWITH TO AN OXIDE OF A LOWER VALENCE STATE, AND THEREAFTER SULFIDING SAID REDUCED MATERIAL. 